Multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulators/initiators

ABSTRACT

The instant invention relates to multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulatros/initiators. Further subjects of the invention are a polymerizable composition comprising an ethylenically unsaturated monomer or oligomer and the alkoxyamine compound as well as a process for polymerization and a process for preparation of the compounds.

The instant invention relates to multifunctional alkoxyamines based onpolyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinonesand their use as polymerization regulators/initiators. Further subjectsof the invention are a polymerizable composition comprising anethylenically unsaturated monomer or oligomer and the alkoxyaminecompound as well as a process for polymerization and a process forpreparation of the compounds.

The initiators/regulators, the polymerization processes and resinproducts of the present invention are useful in many applications,including a variety of specialty applications, such as for thepreparation of block copolymers which are useful as compatibilizingagents for polymer blends, or dispersing agents for coating systems orfor the preparation of narrow molecular weight resins or oligomers foruse in coating technologies and thermoplastic films or as toner resinsand liquid immersion development ink resins or ink additives used forelectrophotographic imaging processes.

The concept of having multifunctional alkoxyamines asinitiators/regulators for radical polymerization is known. WO 00/71501for example discloses multifunctional open chain alkoxyamines having aphosphor atom attached to the carbon atom in α-position to the nitrogenatom. The compounds are useful initiators/regulators, however, they arethermally not very stable and can only be used at a polymerizationtemperature of around 120° C. Limited storage stability is a furtherdrawback of these compounds.

U.S. Pat. Nos. 5,627,248 and 5,677,388 disclose difunctionalalkoxyamines on the basis of tetramethylpiperidine. These compounds arenot very reactive and only the polymerization of styrene proceeds withreasonable efficiency at high temperatures. Conversion andpolymerization rate of acrylates is very low.

WO 00/18807 discloses polymeric macroinitiators which have been preparedby ATRP polymerization wherein the halogen atoms have been replaced bynitroxylether end groups.

WO 01/02345 discloses also multifunctional alkoxyamines. These compoundsare all characterized by having a phenyl group attached to the carbonatom in α-position to the oxygen atom of the alkoxyamine group. Thisaromatic group can have drawbacks in the end use of the polymers.Typically photo stability decreases, when aromatic moieties are present.This leads in many cases to discoloration which is undesirable for manyend uses.

Surprisingly, it has now been found that the present compounds are verysuitable to prepare (co)polymers particularly block, star, comb(co)polymers and the like, without having the drawbacks of the prior artcompounds.

By their multiple alkoxyamine functionality they provide an ideal toolfor tailor made polymerization processes. The degree of branches can bechosen by selecting two, three, four or even more alkoxyaminefunctionalities.

Furthermore with the present invention there are providedinitiators/regulators which allow very efficiently to bring into themacromer functional end-groups which come from the initiating radical.The compounds of the present invention thus allow to produce macromersor polymers with a wide variety of functional groups, which was noteasily possible until now.

The functionalized macromers or polymers may then be further reactedwith suitable modifying compounds to further adjust the polymer'sproperties.

Polymerization of the monomers results in a polymer or copolymer ofnarrow polydispersity, higher molecular weight and a high monomer topolymer conversion even at relatively low temperatures and at shortreaction times, making the polymerization process particularly suitablefor industrial applications. The resulting (co)polymers are of highpurity and in many cases colorless, therefore not requiring any furtherpurification. The polymers prepared with the instant compounds show highphoto and thermal stability and exhibit only a minor discoloration uponexposure to UV light and heat due to the higher alkoxyamine content.

One subject of the invention is a compound of formula Ia, Ib, Ic or Id

wherein

R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkyl orphenyl;

R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by OH, orphenyl which is unsubstituted or substituted by OH, halogen, C₁-C₈alkoxyor C₁-C₈alkyl;

X is O, S, NR₄ or, if Z is —O—CH₂—, X is additionally a direct bond;

R₄ is hydrogen or C₁-C₁₈alkyl;

Z is a direct bond and if R₁ is hydrogen and R₂ phenyl, Z isadditionally —O—CH₂—;

Y is a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl;

or if X is a direct bond and Z is —O—CH₂—, Y is a radical derived from apolycarboxylic acid having 2-20 carboxylic functions;

A and A′ together are ═O; or

A′ is hydrogen; and

A is hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl;

or a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH, —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atom, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl)

R₁₀₂ is hydrogen, C₁-C₁₈alkyl or R₁₀₁ and R₁₀₂ together with thenitrogen atom form a 5-membered ring which may have an unsaturated bondor be fused to a benzene ring;

R₁₀₃ is hydrogen or C₁-C₁₈alky; or

A and A′ together are a group

-   -    wherein

Z₁ is O, NR₂₀₂ or when R₂₀₁, represents alkyl or aryl Z₁ is additionallya direct bond;

R₂₀₂ is H, C₁-C₁₈alkyl or phenyl;

R₂₀₁ is H, straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which maybe unsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅-C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl;

phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl; or

—C(O)—C₁-C₁₈alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 9 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;

—SO₃ ⁻Me⁺, —PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂,or Si(Me)₃, wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or

A is O—Y₁ and A′ is O—Y₂ forming a ketale structure in the 4 position;wherein

Y₁ and Y₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl, C₇-C₉phenylalkyl; or

Y₁ and Y₂ together form one of the bivalent groups—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, —CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—,—CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—, —CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene,1,2-cyclohexyliden,

—CH₂—CH═CH—CH₂— or

wherein

R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl or CH₂OR₃₀₄;

R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOH orCOO—(C₁-C₁₂)alkyl;

R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms.

Halogen is F, Cl, Br, I, preferably Cl or Br.

C₁-C₁₈alkyl can be linear or branched. Examples are methyl, ethyl,propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl,hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl ordodecyl.

C₂-C₁₈alkyl interrupted by at least one O atom is for example—CH₂—CH₂—O—CH₂—CH₃, —CH₂—CH₂—O—CH₃ or —CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃.It is preferably derived from polyethlene glycol. A general descriptionis —((CH₂)_(a)—O)_(b)—H/CH₃, wherein a is a number from 1 to 6 and b isa number from 2 to 10.

Further examples of C₂-C₁₈alkyl interrupted by —O— are for example3-oxapentane, 4-oxaheptane, 3,6-dioxaoctane, 4,7-dioxadecane,4,9-dioxadodecane, 3,6,9-trioxaundecane and 4,7,10-trioxatridecane.

Alkyl substituted by a group —COOH is for example CH₂—COOH,CH₂—CH₂—COOH, (CH₂)₃—COOH or CH₂—CHCOOH—CH₂—CH₃

Hydroxyl- or alkoxycarbonyl substituted C₁-C₁₈alkyl can be, for example,2-hydroxyethyl, 2-hydroxypropyl, methoxycarbonylmethyl or2-ethoxycarbonylethyl, 2-hydroxyethyl is preferred.

Alkenyl having from 3 to 18 carbon atoms is a branched or unbranchedradical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,isododecenyl.

Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.

Aryl is phenyl or naphthyl.

C₇-C₉phenylalkyl is for example benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.

C₅-C₁₂cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

C₅-C₁₂cycloalkenyl is for example 3-cyclopentenyl, 3-cyclohexenyl or3-cycloheptenyl.

If R₁ is a monovalent radical of a α, β-unsaturated or aromaticcarboxylic acid, it is, for example, an acryloyl, methacryloyl, benzoylor β-(3,5di-tert-butyl-4-hydroxyphenyl)propionyl radical.

A monovalent radical of an aliphatic carboxylic acid is for exampleacetyl, propionyl, butyryl, caproyl, stearoyl or oleyl.

Preferred is a compound of formula Ia, Ib, Ic or Id wherein

X is O or NR₄, wherein R₄ is hydrogen or C₁-C₈alkyl;

Z is a direct bond;

R₁ is hydrogen or C₁-C₁₈alkyl; and

R₂ is C₁-C₁₈alkyl and the other substituents are as defined above.

More preferred is a compound of formula Ia, Ib, Ic or Id wherein

A and A′ together are ═O; or

A′ is hydrogen and

A is hydrogen, OH, OR₁₀₀, NHR₁₀₀, NR₁₀₀R₁₀₃ or a group

wherein R₁₀₀, R₁₀₁, R₁₀₂ and R₁₀₃ independently are hydrogen orC₁-C₁₈alkyl; or

A is O—Y₁ and A′ is O—Y₂ forming a ketale structure in the 4 position;wherein

Y₁ and Y₂ are independently C₁-C₁₂alkyl, phenyl or benzyl; or

Y₁ and Y₂ together form one of the bivalent groups—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—,—CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—, —CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, or—CH₂—CH═CH—CH₂—, wherein

R₃₀₁ is hydrogen, C₁-C₁₂alkyl or COO—(C₁-C₁₂)alkyl; and

R₃₀₂ and R₃₀₃ are independently hydrogen, methyl ethyl orCOO—(C₁-C₁₂)alkyl.

Y is an organic radical derived from a polyfunctional alcohol,polyfunctional aminoalcohol, polyfunctional amine, polyfunctionalmercaptane, polyfunctional phenol or polyfunctional thiophenol.

The polyfunctional alcohol can be an aliphatic polyfunctional alcohol, acycloaliphatic polyol or an aromatic polyol.

The aliphatic polyfunctional alcohol can contain 2 to 20 carbon atoms,the cycloaliphatic polyols 5 to 12 carbon atoms and the aromatic polyols6 to 18 carbon atoms.

Polyoxyalkylene glycols having a molecular weight from 150 to 40000 canalso be used.

Aromatic polyols are those, wherein at least two hydroxyl groups arebound to one or to different aromatic hydrocarboxylic radicals.

Suitable aliphatic polyols are for example diols which are linear orbranched aliphatic glycols, in particular those containing 2 to 12,preferably 2 to 6, carbon atoms in the molecule, for example: ethyleneglycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 2,3- or1,4-butanediol, pentyl glycol, neopentyl glycol, 1,6-hexanediol,1,12-dodecanediol. A suitable cycloaliphatic diol is, for example,1,4-dihydroxycyclohexane. Other suitable aliphatic diols are, forexample, 1,4-bis(hydroxymethyl)cyclohexane, aromatic-aliphatic diols,such as p-xylylene glycol or 2,5-dichloro-p-xylylene glycol,2,2-(β-hydroxyethoxyphenyl)propane and polyoxyalkylene glycols, such asdiethylene glycol, triethylene glycol, polyethylene glycol orpolypropylene glycol. The alkylenediols are preferably linear andpreferably contain 2 to 4 carbon atoms.

Other suitable diols are the β-hydroxyalkylated, in particularβ-hydroxyethylated bisphenols, such as2,2-bis[4′-(β-hydroxyethoxy)phenyl]propane.

Another group of suitable aliphatic diols are the heterocyclic diolsdescribed in the German published patent specifications 1812003,2342432, 2342372 and 2453326. Examples are:N,N′-bis(β-hydroxyethyl)-5,5-dimethylhydantoin,N,N′-bis(β-hydroxypropyl)-5,5-dimethylhydantoin,methylenebis-[N-(β-hydroxyethyl)-5-methyl-5-ethylhydantoin],methylenebis-[N-(β-hydroxyethyl)-5,5-dimethylhydantoin],N,N′-bis(β-hydroxyethyl)benzimidazolone,N,N′-bis(β-hydroxyethyl)-(tetrachloro)benzimidazolone orN,N′-bis(β-hydroxyethyl)-(tetrabromo)benzimidazolone.

Suitable aromatic diols are mononuclear diphenols and, in particular,dinuclear diphenols carrying a hydroxyl group at each aromatic nucleus.The term aromatic will be taken to mean preferably hydrocarbonaromaticradicals such as phenylene or naphthylene. Besides e.g. hydroquinone,resorcinol or 1,5-, 2,6- and 2,7-dihydroxynaphthalene,9,10-dihydroxyanthracene, 4,4′-dihydroxybiphenyl, bisphenols meritparticular mention.

Examples of bisphenols are: bis(p-hydroxyphenyl) ether orbis(p-hydroxyphenyl) thioether, bis(p-hydroxyphenyl)sulfone,bis(p-hydroxyphenyl)methane, bis(4-hydroxyphenyl)-2,2′-biphenyl,phenylhydroquinone, 1,2-bis(p-hydroxyphenyl)ethane,1-phenyl-bis(p-hydroxyphenyl)methane,diphenyl-bis(p-hydroxyphenyl)methane,diphenyl-bis(p-hydroxyphenyl)ethane,bis(3,5-dimethyl-4-hydroxyphenyl)sulfone,bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene,bis(3,5-dimethyl-4-hydroxyphenyl)-m-diisopropylbenzene,2,2-bis(3′,5′-dimethyl-4′-hydroxyphenyl)propane, 1,1- or2,2-bis(p-hydroxyphenyl)butane,2,2-bis(p-hydroxyphenyl)hexafluoropropane, 1,1-dichloro- or1,1,1-trichloro-2,2-bis(p-hydroxyphenyl)ethane,1,1-bis(p-hydroxyphenyl)cyclopentane and, in particular,2,2-bis(p-hydroxyphenyl)propane (bisphenol-A) and1,1-bis(p-hydroxyphenyl)cyclohexane (bisphenol-C).

A suitable triol is for example

R═CH₂—CH₂—OH.

Other suitable aliphatic triols are for example glycerin ortrimethylolpropane.

Examples for a tetrafunctional alcohol are erythritol, threitol orpentaerythritol.

Higher alcohols are for example pentahydroles, for example xylitol orarabitol and hexahydrols, for example sorbitol, mannitol, dulcitol,talitol, iditol, inositol.

In principal all hydroxylated aliphatic hydrocarbon compounds aresuitable as multifunctional alcohols.

The polyaminoalcohols or polyamines can be deduced from the abovementioned polyalcohols by replacing one or more hydroxyl groups by aminogroups.

Primary amino groups are preferred, which may be attached to aromaticrings or alkyl groups as mentioned above for the corresponding alcohols.

Suitable mercaptanes or thiophenols are those which are derived bysubstituting the oxygen atom by a sulfur atom in the above mentionedexamples.

If X is a direct bond and Z is —O—CH₂—, then Y is a radical derived froma polycarboxylic acid having 2-20 carboxylic functions.

Suitable polycarboxylic acids are for example dicarboxylic acids likeoxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid,adipic acid, 1,12-dodecandioic acid, phthalic-, isophthalic- orterephthalic acid, isomeric naphthalene dicarboxylic acids,tricarboxylic acids like citric acid, nitrilotriacetic acid or1,2,4-benzentricarboxylic acid, tetracarboxylic acids likeethylenediamine tetraacetic acid or pyromellitic acid, pentacarboxylicacids like for example diethylenetriaminepentaacetic acid,hexacarboxylic acids like for example mellitic acid ortriethylenetetraminehexaacetic acid.

Preferably Y is a radical derived from a polyol or polyamine, having 2to 20 —OH or —NR₅H groups, wherein R₅ is hydrogen, C₁-C₁₈alkyl orphenyl.

More preferably Y is an aliphatic polyol. Examples have been alreadymentioned.

Preferably n is a number from 2-20, more preferably from 2-10 and mostpreferably from 2-6.

Most preferred is a compound of formula Ia or Ib, to which thepreferences given above may also apply.

Particularly suitable compounds are

compound 101 of Table 1,

compound 107 of Table 1,

compound 109 of Table 1 and

compound 110 of Table 1.

A further subject of the invention is a polymerizable composition,comprising

a) at least one ethylenically unsaturated monomer or oligomer, and

b) a compound of formula Ia, Ib, Ic or Id or a mixture thereof

wherein

R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkyl orphenyl;

R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by OH, orphenyl which is unsubstituted or substituted by OH, halogen, C₁-C₈alkoxyor C₁-C₈alkyl;

X is O, S, NR₄ or, if Z is —O—CH₂—, X is additionally a direct bond;

R₄ is hydrogen or C₁-C₁₈alkyl;

Z is a direct bond and if R₁ is hydrogen and R₂ phenyl, Z isadditionally —O—CH₂—;

Y is a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl;

or if X is a direct bond and Z is —O—CH₂—, Y is a radical derived from apolycarboxylic acid having 2-20 carboxylic functions;

A and A′ together are ═O; or

A′ is hydrogen; and

A is hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl;

or a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH, —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atom, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl)

R₁₀₂ is hydrogen, C₁-C₁₈alkyl or R₁₀₁, and R₁₀₂ together with thenitrogen atom form a 5-membered ring which may have an unsaturated bondor be fused to a benzene ring;

R₁₀₃ is hydrogen or C₁-C₁₈alkyl; or

A and A′ together are a group

wherein

Z₁ is O, NR₂₀₂ or when R₂₀₁ represents alkyl or aryl Z₁ is additionallya direct bond;

R₂₀₂ is H, C₁-C₁₈alkyl or phenyl;

R₂₀₁ is H, straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which maybe unsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅-C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl;

phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl; or

—C(O)—C₁-C₁₈alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 9 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;

—SO₃ ⁻Me⁺, —PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂,or Si(Me)₃, wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or

A is O—Y, and A′ is O—Y₂ forming a ketale structure in the 4 position;wherein

Y₁ and Y₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl, C₇-C₉phenylalkyl; or

Y₁ and Y₂ together form one of the bivalent groups—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, —CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—,—CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—, —CH₂C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene,1,2-cyclohexyliden,

—CH₂—CH═CH—CH₂— or

wherein

R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl or CH₂OR₃₀₄;

R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOH orCOO—(C₁-C₁₂)alkyl;

R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms.

Definitions and preferences for the individual substituents have beenmentioned above.

Preferably the initiator/regulator compound of formula (Ia), (Ib), (Ic)or (Id) is present in an amount of from 0.01 mol-% to 20 mol-% morepreferably in an amount of from 0.01 mol-% to 10 mol-% and mostpreferred in an amount of from 0.05 mol-% to 10 mol-% based on themonomer or monomer mixture.

It is also possible to use a mixture of different initiators/regulators.

When monomer mixtures are used mol-% is calculated on the averagemolecular weight of the mixture.

Preferably the ethylenically unsaturated monomer or oligomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,n-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (meth)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

Particularly the ethylenically unsaturated monomers are ethylene,propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene,α-C₅-C₁₈alkene, styrene, α-methyl styrene, p-methyl styrene or acompound of formula CH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Z is oxygen or sulfur.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

wherein An⁻ and R_(a) have the meaning as defined above and R_(e) ismethyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

Particularly preferred ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

A further subject of the invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block or random) byfree radical polymerization of at least one ethylenically unsaturatedmonomer or oligomer, which comprises (co)polymerizing the monomer ormonomers/oligomers in the presence of an initiator compound of formula(Ia), (Ib), (Ic) or (Id) under reaction conditions capable of effectingscission of the O—C bond to form two free radicals, the radical

being capable of initiating polymerization.

Preferred is a process wherein the scission of the O—C bond is effectedby ultrasonic treatment, heating or exposure to electromagneticradiation, ranging from γ to microwaves.

More preferably the scission of the O—C bond is effected by heating andtakes place at a temperature of between 50° C. and 160° C.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

Preferred processes use as little solvents as possible. In the reactionmixture it is preferred to use more than 30% by weight of monomer andinitiator, particularly preferably more than 50% and most preferrablymore than 80%.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons(chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethyleneglycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexylacetate) and ethers (diethyl ether, dibutyl ether, ethylene glycoldimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The process is particularly useful for the preparation of blockcopolymers.

Block copolymers are, for example, block copolymers of polystyrene andpolyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are usefull as adhesives oras compatibilizers for polymer blends or as polymer toughening agents.Poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers)are useful as dispersing agents for coating systeme, as coatingadditives (e.g. rheological agents, compatibilizers, reactive diluents)or as resin component in coatings (e.g. high solid paints) Blockcopolymers of styrene, (meth)acrylates and/or acrylontrile are usefulfor plastics, elastomers and adhesives.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends.

The (co)polymers of the present invention may have a number averagemolecular weight from 1 000 to 400 000 g/mol, preferably from 2000 to250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol. Whenproduced in bulk, the number average molecular weight may be up to 500000 (with the same minimum weights as mentioned above). The numberaverage molecular weight may be determined by size exclusionchromatography (SEC), gel permeation chromatography (GPC), matrixassisted laser desorption/ionization mass spectrometry (MALDI-MS) or, ifthe initiator carries a group which can be easily distinguished from themonomer(s), by NMR spectroscopy or other conventional methods.

The polymers or copolymers of the present invention have preferably apolydispersity of from 1.0 to 2, more preferably of from 1.1 to 1.9 andmost preferably from 1.1 to 1.8.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranched and dendriticcopolymers, as well as graft or copolymers.

The polymers prepared by the present invention are useful for followingapplications:

adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers,adhesion promoters, corrosion inhibitors, viscosity improvers,lubricants, rheology modifiers, thickeners, crosslinkers, papertreatment, water treatment, electronic materials, paints, coatings,photography, ink materials, imaging materials, superabsorbants,cosmetics, hair products, preservatives, biocide materials or modifiersfor asphalt, leather, textiles, ceramics and wood.

Because the present polymerizaton is a “living” polymerization, it canbe started and stopped practically at will. Furthermore, the polymerproduct retains the functional alkoxyamine group allowing a continuationof the polymerization in a living matter. Thus, in one embodiment ofthis invention, once the first monomer is consumed in the initialpolymerizing step a second monomer can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different monomer(s) to prepare multi-block copolymers.

Furthermore, since this is a radical polymerization, blocks can beprepared in essentially any order. One is not necessarily restricted topreparing block copolymers where the sequential polymerizing steps mustflow from the least stabilized polymer intermediate to the moststabilized polymer intermediate, such as is the case in ionicpolymerization. Thus it is possible to prepare a multi-block copolymerin which a polyacrylonitrile or a poly(meth)acrylate block is preparedfirst, then a styrene or butadiene block is attached thereto, and so on.

Furthermore, there is no linking group required for joining thedifferent blocks of the present block copolymer. One can simply addsuccessive monomers to form successive blocks.

A plurality of specifically designed polymers and copolymers areaccessible by the present invention, such as star and graft (co)polymersas described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107,pages 1623-1627, dendrimers as described by K. Matyaszewski et al. inMacrmolecules 1996, Vol 29, No. 12, pages 4167-4171, graft (co)polymersas described by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155-166(1997), random copolymers as described by C. J. Hawker inMacromolecules 1996, 29, 2686-2688, or diblock and triblock copolymersas described by N. A. Listigovers in Macromolecules 1996, 29, 8992-8993.

A further subject of the invention is the use of a compound of formulaIa, Ib, Ic or Id for the controlled radical (co)polymerization ofethylenically unsaturated monomers.

The compounds of formula Ia, Ib, Ic and Id are prepared according to thefollowing reaction scheme which is illustrative for a compound offormula Ia:

The nitroxyl compounds are known and can be prepared by known methods.Their preparation is for example described in GB 2335190, GB 2342649,and GB 2 361 235.

Hal is halogen and preferably Br or Cl.

Multifunctional halogenated compounds can be prepared for example byreacting a α-halogenated acid chloride or bromide with a polyfunctionalalcohol, polyfunctional aminoalcohol, polyfunctional amine,polyfunctional mercaptane or polyfunctional phenol. The preparation ofmultifunctional halogenated compounds from polyfunctional alcohols and aα-halogenated acid chloride is for example described in WO 00/43344.

If X is a direct bond and Z is —O—CH₂—, then the the multifunctionalcompounds may be prepared for example by reacting a suitable derivativeof a polycarboxylic acid, for example an acid chloride with thecorresponding alcohol according the equation:

The above educts are reacted to the compounds according to formula Ia,Ib, Ic and Id in conventional solvents, such as for examples cyclicethers in accordance with the method described by Matyjaszewski in U.S.Pat. No. 5,910,549.

A drawback of the process described in U.S. Pat. No. 5,910,549 is, thatan excess of the nitroxyl compound has to be used which remains in theend product. A separation and purification is in most cases onlypossible by chromatography.

Since remaining nitroxyl radicals adversly affect the rate of thepolymerization reaction, it is highly desirable to remove those radicalsin an industrially feasible way. This problem has been solved by thepresent invention by applying a reducing step at the end of thereaction. The excess nitroxyl is reduced to the correspondinghydroxylamine or amine which both are more basic than the nitroxyl andthus can be washed out by an acid washing step.

Surprisingly the alkoxyamine remains unaffected and the yields remainhigh. The improvement is particularly useful in view of an industrialproduction of such compounds.

A further subject of the invention is therefore a process for thepreparation of a compound of formula Ia, Ib, Ic or Id which processcomprises the steps of

a) reacting a compound of formula IIa, IIb, IIc or IId

with a compound of formula III

having a radically transferable group Hal, with a transition metalcomplex in the absence of oxygen;

b) subjecting the reaction mixture to a reduction step;

c) washing the resulting mixture with an aqueous acid solution and

d) isolating the product.

The definitions and preferences for the compounds of formula Ia, Ib, Icand Id have already been given and apply also for the other subjects ofthe invention.

Complexing agents are known and for example described in U.S. Pat. No.5,910,549.

The reduction step can be performed by various methods, such as forexample by catalytic hydrogenation, with hydrazine or dithionite.Preferred is a reduction with Na-dithionite.

The Na-dithionite is preferably used as an aqueous solution or as apowder. The concentration of the aqueous solution may vary from 0.1% to40% by weight, preferred is 5% to 20%.

The acid used in the washing step is preferably a mineral acid, such asHCl, but also organic sulfonic acids or complex acids such HPF₈ or HClO₄are suitable.

The reaction temperature is preferably from 0° C. to 80° C., morepreferably from 10° C. to 50° C.

The reaction time can vary in a wide range from 30 minutes to 24 hours,depending on the educts. In most cases 2 hours to 16 hours aresufficient to complete the reaction.

The reaction is usually carried out under normal conditions. However insome cases a slight pressure of up to 1 bar or a slight evacuation to200 mbar may be of advantage.

The coupling reaction per se is known and the concentrations of thereactants may vary in a wide range as described in U.S. Pat. No.5,910,549.

The following examples illustrate the invention.

A) PREPARATION EXAMPLES Example A1 Compound 101

In a 100 ml three neck flask 7.75 g (36.1 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl (preparedaccording to DE 199 09 767 A1, example 2), 5.19 g (36.1 mmol) Cu(I)Brand 2.29 g (36.1 mmol) Cu(O)-powder are added. Oxygen is removed fromthe reaction mixture by applying vacuum and flushed with nitrogen. 50 mldioxane and 6.0 g (18.1 mmol) 1,2-ethandiolbis(2-brompropionate) areadded under stirring homogenized (suspension of CuBr and Cu in dissolvededukts). With a syringe 12.53 g (72.3 mmol)N,N,N′,N″,N″-Pentamethyldiethylentriamine (PMDETA) are slowly added andthe exothermal reaction started. The temperature is kept at 20° C. withan ice bath. During the reaction the color of the suspension changesfrom red to green. After 12 h stirring at 20° C. After stirring for 12 hat 20° C. the reaction is stopped and the reaction mixture is filteredover Tonsil Supreme 110FF (Süd Chemie). The filtrate is concentratedunder vacuum and 50 ml aetylacetate are added: The solution is washedtwice with 30 ml of a 10% EDTA-solution (ethylandiamin tetraacetic aciddisodium salt), subsequently twice with 20 ml of a 10% freshly preparedsodium dithionite solution and finally once with 20 ml of a 0.1 n HCl.The organic phase is dried over Na₂SO₄, filtered off and the filtrate isconcentrated and dried at 60° C. under vacuum. 6.7 g (62%) of compound101 are obtained as a slightly yellow resinous product.

Elemental Analysis: Calculated C₃₂H₆₀N₂O₈: C 63.97%, H 10.07%, N 4.66%;Found: C 63.07%, H 10.05%, N 4.38%.

Example A2 Compound 102

In analogy to example A1 4.28 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.87 g (20mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol) PMDETAare reacted in 40 ml dioxane with 4.14 g (10 mmol)1,4-cyclohexandiolbis(2-brompropionate). 6.4 g (97%) of compound 102 areobtained as slightly yellow solid resin.

Elemental Analysis: Calculated C₃₈H₆₆N₂O₈: C 66.02%, H 10.16%, N 4.28%;Found: C 65.63%, H 10.04%, N 4.11%.

Example A3 Compound 103

In analogy to example 1 4.28 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.87 g (20mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol) PMDETAare reacted in 40 ml dioxane with 3.86 g (10 mmol)N,N′-Bis-(2-brompropionyl)-1,6-diaminohexane. 5.5 g (84%) of compound103 are obtained as white solid resin.

Elemental Analysis: Calculated C₃₈H₇₀N₄O₆: C 66.02%, H 10.77%, N 8.55%;Found: C 65.33%, H 10.70%, N 8.12%.

Example A4 Compound 104

In analogy to example 1 4.25 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidine-1-oxyl, 2.87 g (20 mmol)Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol) PMDETA arereacted in 40 ml dioxane with 3.86 g (10 mmol)N,N′-Bis-(2-brompropionyl)-1,6-diaminohexane. 5.6 g (85%) of compound104 are obtained as pale white solid resin.

Elemental Analysis: Calculated C₃₈H₇₀N₄O₆: C 66.43%, H 10.22%, N 8.61%;Found: C 66.01%, H 9.90%, N 8.22%.

Example A5 Compound 105

In analogy to example 1 4.28 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.87 g (20mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol) PMDETAare reacted in 40 ml dioxane with 6.24 g (10 mmol) poly(ethyleneglycole-400)-bis(2-brompropionate). 5.7 g (67%) of compound 105 areobtained as pale white solid resin.

Example A6 Compound 106

In analogy to example 1 4.28 g (20 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.87 g (20mmol) Cu(I)Br, 1.27 g (20 mmol) Cu(O)-powder and 6.93 g (40 mmol) PMDETAare reacted in 40 ml dioxane with 6.24 g (10 mmol)poly(tetrahydrofuran-250)-bis(2-brompropionate). 6.1 g (77%) of compound106 are obtained as pale white solid resin.

Example A7 Compound 107

In analogy to example A1 3.21 g (15 mmol)2,6-Diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.15 g (15mmol) Cu(I)Br, 191 mg (3 mmol) Cu(O)-powder and 2.60 g (0.15 mmol)PMDETA are reacted in 15 ml ethylacetate with 2.69 g (5 mmol)tris-(2′-brompropionyl)-1,1,1-trimethylolpropane (prepared according toWO 00/43344) for 20 h at R.T. 2.42 g (51%) of compound 108 are obtainedas a white powder.

Elemental Analysis: Calculated C₅₁H₉₅N₃O₁₂: C 65.01%, H 10.16%, N 4.46%;Found: C 63.69%, H 9.86%, N 4.40%. Maldi-TOF-MS: M⁺: 942 (ascalculated).

Example A8 Compound 108

In analogy to example 1 3.21 g (15 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.15 g (15mmol) Cu(I)Br, 191 mg (3 mmol) Cu(O)-powder and 2.60 g (15 mmol) PMDETAin 15 ml ethylacetate are reacted with 2.86 g (5 mmol)Tris-(2′-brompropionyl)phloroglucine (prepared in accordance with WO00/43344) for 18 h at R.T. 4.05 g (83%) of compound 109 are obtained asa white orange powder.

Example A9 Compound 109

In analogie to example 1 4.28 g (20 mmol)2,6-Diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 2.87 g (20mmol) Cu(I)Br, 318 mg (5 mmol) Cu(O)-powder and 3.46 g (20 mmol) PMDETAin 15 ml ethylacetate are reacted with 3.38 g (5 mmol)tetrakies-(2′-brompropionyl)-pentaerythrite (prepared in accordance withWO 00/43344) umgesetzt (20 h, R.T.). 4.75 g (78%) of compound 110 areobtained as a white powder.

Elemental Analysis: Calculated C₆₅H₁₂₀N₄O₁₆: C 64.38%, H 9.97%, N 4.62%;Found: C 63.75%, H 9.76%, N 4.49%. Maldi-TOF-MS: M⁺: 1213 (ascalculated).

Example A10 Compound 110

In analogy to example 1 2.57 g (12 mmol)2,6-diethyl-2,3,6-trimethyl-4-hydroxy-piperidine-1-oxyl, 1.18 g (12mmol) Cu(I)Cl, 152 mg (2.4 mmol) Cu(O)-powder and 2.08 g (12 mmol)PMDETA in 15 ml ethylacetate are reacted with 1.45 g (2 mmol)Hexakis-(2′-chlorpropionyl)sorbitol (prepared in accordance with WO00/43344) for 15 h at R.T. 3.0 g (84%) of compound 111 are obtained asan off white powder.

Elemental Analysis: Calculated C₉₆H₁₇₆N₆O₂₄: C 64.11%, H 9.86%, N 4.67%;Found: C 63.20%, H 9.57%, N 4.25%.

Example A111 Compound 111

In analogy to example A1 3.06 g (12 mmol)1-t-butyl-3,3-diethyl-5,5-dimethylpiperazin-2-on-4-oxyl (prepared inaccordance with DE 19949352 A1, example B38), 1.72 g (12 mmol) Cu(I)Br,0.76 g (12 mmol) Cu(O)-powder and 4.24 g (24 mmol) PMDETA are reacted in25 ml toluene with 1.99 g (6 mmol) 1,2-ethandiolbis(2-brompropionate).1.96 g (48%) of compound 111 are obtained as a colorless resinousproduct.

Elemental Analysis: Calculated C₃₈H₈₈N₄O₈; C 63.31%, H 9.74%, N 8.20%;Found: C 63.09%, H 9.58%, N 7.77%.

Example A112 Compound 112

In analogy to example A1 5.0 g (25 mmol) 3,3-diethyl-5,5dimethylmorpholin-2-on-4-oxyl (prepared in accordance with DE 19949352A1, example B8), 3.70 g (25 mmol) Cu(I)Br, 1.60 g (25 mmol) Cu(O)-powderand 8.84 g (50 mmol) PMDETA are reacted in 50 ml toluene with 4.15 g(12.5 mmol) 1,2-ethandiolbis(2-brompropionate). 6.57 g (92%) of compound112 are obtained as a colorless resinous product.

Elemental Analysis: Calculated C₂₈H₄₈N₂O₁₀; C 58.72%, H 8.45%, N 4.89%;Found: C 58.98%, H 8.46%, N 4.78%.

The compounds are summarized in Table 1.

TABLE 1 Compounds prepared Compound no. Structure 101

102

103

104

105

106

107

108

109

110

111

112

B POLYMERIZATION EXAMPLES Polymerization Examples in Styrene

General Remarks:

Styrene and the other monomers are distilled over a Vigreux column undervacuum, shortly before being used.

To remove oxygen all polymerization reaction mixtures are flushed beforepolymerization with argon and evacuated under vaccum applying afreeze-thaw cycle. The reaction mixtures are then polymerized underargon atmosphere.

At the start of the polymerization reaction, all starting materials arehomogeneously dissolved.

Conversion is determined by removing unreacted monomers from the polymerin a vacuum oven at 70° C. and 0.01 torr for at least 24 hours, weighingthe remaining polymer and subtracting the weight of the initiator.

Characterization of the polymers is carried out by GPC (Gel PermeationChromatography).

GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS. Tetrahydrofuran(THF) is used as a solvent and is pumped at 1 ml/min. Two chromatographycolumns are put in series: type Plgel 5 μm mixed-C of POLYMERINSTRUMENTS, Shropshire, UK. Measurements are performed at 40° C. Thecolumns are calibrated with low polydispersity polystyrenes having Mnfrom 200 to 2 000 000 Dalton. Detection is carried out using aRI-Detector or UV-Detector at 30° C.

Example B1 Polymerization of Styrene with 0.5 mol % of Compound 102(Table 1) at 130° C.

In a 100 ml schlenck flask, equipped with magnetic stirrer, 0.972 g(1.48 mmol) of compound 102 and 30.9 g (297 mmol) of styrene are mixedand degassed. The clear solution obtained is stirred under argon at 130°C. and polymerization is carried out during 6 h. The reaction mixture isthen cooled to RT. The remaining monomer is removed by evaporation underhigh vacuum at 70° C. 21.8 g (70.6%) of the initial monomer havereacted. A slightly yellow solid is obtained.

Mn=13780, Mw=17360, PD=1.26

Example B2 Polymerization of Styrene with 0.5 mol % of Compound 103(Table 1) at 130° C.

In a 100 ml schlenck flask, equipped with magnetic stirrer, 0.974 g(1.49 mmol) of compound 103 and 31.0 g (297 mmol) of styrene are mixedand degassed. The clear solution obtained is stirred under argon at 130°C. and polymerization is carried out during 6 h. The reaction mixture isthen cooled to RT. The remaining monomer is removed by evaporation underhigh vacuum at 70° C. 22.7 g (73.4%) of the initial monomer havereacted. A white solid is obtained.

Mn=1520, Mw=23980, PD=1.58

Example B3 Polymerization of Styrene with 0.5 mol % of Compound 104(Table 1) at 130° C.

In a 100 ml schlenck flask, equipped with magnetic stirrer, 0.525 g(0.81 mmol) of compound 104 and 16.8 g (161 mmol) of styrene are mixedand degassed. The clear solution obtained is stirred under argon at 130°C. and polymerization is carried out during 6 h. The reaction mixture isthen cooled to RT. The remaining monomer is removed by evaporation underhigh vacuum at 70° C. 13.1 g (78.1%) of the initial monomer havereacted. A white solid is obtained.

Mn=17420, Mw=25550, PD=1.47

Polymerization Examples in Acrylates Example B4 Polymerization of n-BuAwith Compound 102 (Table 1)

A round-bottom three necked flask, equipped with thermometer, condenserand magnetic stirrer is charged with 0.383 g (0.59 mmol) of compound 102and 10 g (78 mmol) of n-butylacrylate and degassed. The clear solutionis then heated to 145° C. under argon. The mixture is stirred for 5hours at 145° C. and then cooled to 60° C. and the remaining monomer isevaporated under high vacuum. 7.9 g (79%) of the monomer are reacted anda yellow turbid viscous liquid is obtained.

GPC: Mn=11000, Mw=15070, Polydispersity index=1.37

Example B5 Polymerization of n-BuA with Compound 103 (Table 1)

A round-bottom three necked flask, equipped with thermometer, condenserand magnetic stirrer is charged with 0.383 g (0.59 mmol) of compound 103and 10 g (78 mmol) of n-butylacrylate and degassed. The clear solutionis then heated to 145° C. under argon. The mixture is stirred for 5hours at 145° C. and then cooled to 60° C. and the remaining monomer isevaporated under high vacuum. 7.9 g (79%) of the monomer are reacted anda yellow viscous liquid is obtained.

GPC: Mn=11650, Mw=17475, Polydispersity index=1.5

Example B6 Polymerization of n-BuA with Compound 111

A round-bottom three necked flask, equipped with thermometer, condenserand magnetic stirrer is charged with 0,403 g (0.59 mmol) of compound 111and 10 g (78 mmol) of n-buthylacrylate and degassed. The clear solutionis then heated to 145° C. under argon. The mixture is stirred for 5hours at 145° C. and then cooled to 60° C. and the remaining monomer isevaporated under high vacuum. 7.2 g (72%) of the monomer are reacted anda yellow viscous liquid is obtained.

GPC: Mn=9710, Mw=12050, polydispersity index PD=1.24

Example B7 Polymerization of n-BuA with Compound 112

A round-bottom three necked flask, equipped with thermometer, condenserand magnetic stirrer is charged with 0.338 g (0.59 mmol) of compound 112and 10 g (78 mmol) of n-buthylacrylate and degassed. The clear solutionis then heated to 145° C. under argon. The mixture is stirred for 5hours at 145° C. and then cooled to 60° C. and the remaining monomer isevaporated under high vacuum. 7.8 g (78%) of the monomer are reacted anda yellow viscous liquid is obtained.

GPC: Mn=9890, Mw=12960, polydispersity index PD=1.31

1. A compound of formula Ia, Ib, Ic or Id

wherein R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkylor phenyl; R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby OH, or phenyl which is unsubstituted or substituted by OH, halogen,C₁-C₈alkoxy or C₁-C₈alkyl; X is O, S, NR₄ or, if Z is —O—CH₂—, X isadditionally a direct bond; R₄ is hydrogen or C₁-C₁₈alkyl; Z is a directbond or, if R₁ is hydrogen and R₂ phenyl, Z is additionally —O—CH₂—; Yis a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl; or if X is a direct bond and Z is—O—CH₂—, Y is a radical derived from a polycarboxylic acid having 2-20carboxylic functions; A and A′ together are ═O; or A′ is hydrogen; and Ais hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl; or is a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH or —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atoms, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl); R₁₀₂ is hydrogen or C₁-C₁₈alkylor R₁₀₁ and R₁₀₂ together with the nitrogen atom form a 5-membered ringwhich may have an unsaturated bond or be fused to a benzene ring; R₁₀₃is hydrogen or C₁-C₁₈alky; or A and A′ together are a group

wherein Z₁ is O or NR₂₀₂, or when R₂₀₁ represents alkyl or aryl, Z₁ isadditionally a direct bond; R₂₀₂ is H, C₁-C₁₈alkyl or phenyl; R₂₀₁ is H,straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which may beunsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl groups;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy, carboxyor C₁-C₈alkoxycarbonyl groups; or —C(O)—C₁-C₁₈alkyl, or an acyl moietyof a α,β-unsaturated carboxylic acid having 3 to 9 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Me⁺,—PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂, or Si(Me)₃,wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or A is O—Y₁ andA′ is O—Y₂ forming a ketal structure in the 4 position; wherein Y₁ andY₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl or C₇-C₉phenylalkyl; or Y₁ and Y₂together form one of the bivalent groups —C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—,—CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—, —CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—,—CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene, 1,2-cyclohexylidene,—CH₂—CH═CH—CH₂— or

 wherein R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl orCH₂OR₃₀₄; R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOHor COO—(C₁-C₁₂)alkyl; and R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl or amonovalent acyl residue derived from an aliphatic, cycloaliphatic oraromatic monocarboxylic acid having up to 18 carbon atoms; and n is anumber from 2-20.
 2. A compound of formula Ia, Ib, Ic or Id according toclaim 1 wherein X is O or NR₄, wherein R₄ is hydrogen or C₁-C₈alkyl; Zis a direct bond; R₁ is hydrogen or C₁-C₁₈alkyl; and R₂ is C₁-C₁₈alkyl.3. A compound of formula Ia, Ib, Ic or Id according to claim 1 wherein Aand A′ together are ═O; or A′ is hydrogen and A is hydrogen, OH, OR₁₀₀,NHR₁₀₀, NR₁₀₀R₁₀₃ or a group

wherein R₁₀₀, R₁₀₁, R₁₀₂ and R₁₀₃ independently are hydrogen orC₁-C₁₈alkyl; or A is O—Y, and A′ is O—Y₂ forming a ketal structure inthe 4 position; wherein Y₁ and Y₂ are independently C₁-C₁₂alkyl, phenylor benzyl; or Y₁ and Y₂ together form one of the bivalent groups—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—,—CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—, —CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, or—CH₂—CH═CH—CH₂—, wherein R₃₀₁ is hydrogen, C₁-C₁₂alkyl orCOO—(C₁-C₁₂)alkyl; and R₃₀₂ and R₃₀₃ are independently hydrogen, methylethyl or COO—(C₁-C₁₂)alkyl.
 4. A compound of formula Ia, Ib, Ic or Idaccording to claim 1 wherein Y is a radical derived from a polyol or apolyamine having 2 to 20 —OH or —NR₅H groups, wherein R₅ is hydrogen,C₃-C₁₈alkyl or phenyl.
 5. A compound of formula Ia, Ib, Ic or Idaccording to claim 4 wherein Y is an aliphatic polyol.
 6. A compound offormula Ia, Ib, Ic or Id according to claim 1 wherein n is a number from2-10.
 7. A compound of formula Ia, Ib, Ic or Id according to claim 6wherein n is a number from 2 to
 6. 8. A compound of formula Ia or Ibaccording to claim
 1. 9. A polymerizable composition, comprising a) atleast one ethylenically unsaturated monomer or oligomer, and b) acompound of formula Ia, Ib, Ic or Id or a mixture thereof

wherein R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkylor phenyl; R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby OH, or phenyl which is unsubstituted or substituted by OH, halogen,C₁-C₈alkoxy or C₁-C₈alkyl; X is O, S, NR₄ or, if Z is —O—CH₂—, X isadditionally a direct bond; R₄ is hydrogen or C₁-C₁₈alkyl; Z is a directbond or, if R₁ is hydrogen and R₂ phenyl, Z is additionally —O—CH₂—; Yis a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl; or if X is a direct bond and Z is—O—CH₂—, Y is a radical derived from a polycarboxylic acid having 2-20carboxylic functions; A and A′ together are ═O; or A′ is hydrogen; and Ais hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl; or is a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH or —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atoms, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl); R₁₀₂ is hydrogen or C₁-C₁₈alkylor R₁₀₁ and R₁₀₂ together with the nitrogen atom form a 5-membered ringwhich may have an unsaturated bond or be fused to a benzene ring; R₁₀₃is hydrogen or C₁-C₁₈alky; or A and A′ together are a group

 wherein Z₁ is O or NR₂₀₂, or when R₂₀₁ represents alkyl or aryl, Z₁ isadditionally a direct bond; R₂₀₂ is H, C₁-C₁₈alkyl or phenyl; R₂₀₁ is H,straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which may beunsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅-C₁₂cycloalkyl or C₅C₁₂cycloalkenyl groups;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy, carboxyor C₁-C₈alkoxycarbonyl groups; or —C(O)—C₁-C₁₈alkyl, or an acyl moietyof a α,β-unsaturated carboxylic acid having 3 to 9 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Me⁺,—PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂, or Si(Me)₃,wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or A is O—Y₁ andA′ is O—Y₂ forming a ketal structure in the 4 position; wherein Y₁ andY₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl or C₇-C₉phenylalkyl; or Y₁ and Y₂together form one of the bivalent groups —C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—,—CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—, —CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—,—CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene, 1,2-cyclohexylidene,—CH₂—CH═CH—CH₂— or

 wherein R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl orCH₂OR₃₀₄; R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOHor COO—(C₁-C₁₂)alkyl; and R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl or amonovalent acyl residue derived from an aliphatic, cycloaliphatic oraromatic monocarboxylic acid having up to 18 carbon atoms; and n is anumber from 2-20.
 10. A composition according to claim 9, wherein theethylenically unsaturated monomer or oligomer is selected from the groupconsisting of ethylene, propylene, n-butylene, i-butylene, styrene,substituted styrene, conjugated dienes, acrolein, vinyl acetate,vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylicacidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters,(meth)acrylonitriles, (alkyl)acrylamides, vinyl halides and vinylidenehalides.
 11. A composition according to claim 9, wherein theethylenically unsaturated monomers are ethylene, propylene, n-butylene,i-butylene, isoprene, 1,3-butadiene, α-C₅-C₁₈alkene, styrene, α-methylstyrene, p-methyl styrene or a compound of formulaCH₂═C(R_(a))—(C═Z)—R_(b), wherein R_(a) is hydrogen or C₁-C₄alkyl, R_(b)is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxyinterrupted by at least one N and/or O atom, hydroxy-substitutedC₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino, di(C₁-C₄₈alkyl)amino,hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituteddi(C₁-C₁₈alkyl)amino, —O—CH₂CH₂N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻; An⁻is an anion of a monovalent organic or inorganic acid; Me is amonovalent metal atom or the ammonium ion and Z is oxygen or sulfur. 12.A composition according to claim 9, wherein the compound of formula Ia,Ib, Ic or Id is present in an amount of from 0.01 mol-% to 20 mol-%. 13.A process for preparing an oligomer, a cooligomer, a polymer or acopolymer (block or random) by free radical polymerization of at leastone ethylenically unsaturated monomer or oligomer, which comprises(co)polymerizing the monomers or oligomers in the presence of aninitiator compound of formula Ia, Ib, Ic or Id under reaction conditionscapable of effecting scission of the O—C bond to form two free radicals,the radical

being capable of initiating polymerization, wherein the compounds offormula Ia, Ib, Ic or Id are

wherein R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkylor phenyl; R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby OH, or phenyl which is unsubstituted or substituted by OH, halogen,C₁-C₈alkoxy or C₁-C₈alkyl; X is O, S, NR₄ or, if Z is —O—CH₂—, X isadditionally a direct bond; R₄ is hydrogen or C₁-C₁₈alkyl; Z is a directbond or, if R₁ is hydrogen and R₂ phenyl, Z is additionally —O—CH₂—; Yis a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl; or if X is a direct bond and Z is—O—CH₂—, Y is a radical derived from a polycarboxylic acid having 2-20carboxylic functions; A and A′ together are ═O; or A′ is hydrogen; and Ais hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl; or is a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH or —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atoms, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl); R₁₀₂ is hydrogen or C₁-C₁₈alkylor R₁₀₁ and R₁₀₂ together with the nitrogen atom form a 5-membered ringwhich may have an unsaturated bond or be fused to a benzene ring; R₁₀₃is hydrogen or C₁-C₁₈alky; or A and A′ together are a group

 wherein Z₁ is O or NR₂₀₂, or when R₂₀₁ represents alkyl or aryl, Z₁ isadditionally a direct bond; R₂₀₂ is H, C₁-C₁₈alkyl or phenyl; R₂₀₁ is H,straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which may beunsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl groups;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy, carboxyor C₁-C₈alkoxycarbonyl groups; or —C(O)—C₁-C₁₈alkyl, or an acyl moietyof a α,β-unsaturated carboxylic acid having 3 to 9 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Me⁺,—PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂, or Si(Me)₃,wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or A is O—Y₁ andA′ is O—Y₂ forming a ketal structure in the 4 position; wherein Y₁ andY₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl or C₇-C₉phenylalkyl; or Y₁ and Y₂together form one of the bivalent groups —C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—,—CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—, —CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—,—CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene, 1,2-cyclohexylidene,—CH₂—CH═CH—CH₂— or

 wherein R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl orCH₂OR₃₀₄; R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOHor COO—(C₁-C₁₂)alkyl; and R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl or amonovalent acyl residue derived from an aliphatic, cycloaliphatic oraromatic monocarboxylic acid having up to 18 carbon atoms; and n is anumber from 2-20.
 14. A process according to claim 13, wherein thescission of the O—C bond is effected by heating and takes place at atemperature of between 50° C. and 160° C.
 15. A process for thepreparation of a compound of formula Ia, Ib, Ic or Id, which processcomprises the steps of a) reacting a compound of formula IIa, IIb, IIcor IId

 with a compound of formula III

 having a radically transferable group Hal, with a transition metal ortransition metal compound in the absence of oxygen; b) subjecting thereaction mixture to a reduction step; and c) washing the resultingmixture with an aqueous acid solution and isolating the product; whereinthe compounds of formula Ia, Ib, Ic or Id are

wherein R₁ and R₂ are independently of each other hydrogen, C₁-C₁₈alkylor phenyl; R₃ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substitutedby OH, or phenyl which is unsubstituted or substituted by OH, halogen,C₁-C₈alkoxy or C₁-C₈alkyl; X is O, S, NR₄ or, if Z is —O—CH₂—, X isadditionally a direct bond; R₄ is hydrogen or C₁-C₁₈alkyl; Z is a directbond or, if R₁ is hydrogen and R₂ phenyl, Z is additionally —O—CH₂—; Yis a radical derived from a polyol, a polyamine, a polyaminoalcohol, apolyaminothiol, a polyhydroxythiol, a polyaminohydroxythiol or apolythiol having 2 to 20 —OH, SH and/or —NR₅H groups, wherein R₅ ishydrogen, C₁-C₁₈alkyl or phenyl; or if X is a direct bond and Z is—O—CH₂—, Y is a radical derived from a polycarboxylic acid having 2-20carboxylic functions; A and A′ together are ═O; or A′ is hydrogen; and Ais hydrogen, —O—R₁₀₀, wherein R₁₀₀ is hydrogen, C₁-C₁₈alkyl which isuninterrupted or interrupted by one or more oxygen atoms, NHR₁₀₀,NR₁₀₀R₁₀₃ or cyanoethyl; or is a group

R₁₀₁ is hydrogen, —COOH, —COO(C₁-C₄alkyl), —COO-phenyl, —COObenzyl,C₁-C₈alkoxy, C₁-C₁₈alkyl, C₂-C₄alkenyl, C₁-C₁₈alkyl or C₂-C₄alkenylsubstituted by OH, —COOH or —COO(C₁-C₄)alkyl, C₂-C₁₈alkyl which may beinterrupted by one or more oxygen atoms, unsubstituted cyclopentyl,cyclohexyl, cyclohexenyl, phenyl or naphthyl; or cyclopentyl,cyclohexyl, cylohexenyl, phenyl or naphthyl which are substituted byC₁-C₄alkyl, —COOH or —COO—(C₁-C₄alkyl); R₁₀₂ is hydrogen or C₁-C₁₈alkylor R₁₀₁ and R₁₀₂ together with the nitrogen atom form a 5-membered ringwhich may have an unsaturated bond or be fused to a benzene ring; R₁₀₃is hydrogen or C₁-C₁₈alky; or A and A′ together are a group

 wherein Z₁ is O NR₂₀₂, or when R₂₀₁ represents alkyl or aryl, Z₁ isadditionally a direct bond; R₂₀₂ is H, C₁-C₁₈alkyl or phenyl; R₂₀₁ is H,straight or branched C₁-C₁₈alkyl or C₃-C₁₈alkenyl, which may beunsubstituted or substitued, by one or more OH, C₁-C₈alkoxy, carboxy,C₁-C₈alkoxycarbonyl, C₅C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl groups;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy, carboxyor C₁-C₈alkoxycarbonyl groups; or —C(O)—C₁-C₁₈alkyl, or an acyl moietyof a α,β-unsaturated carboxylic acid having 3 to 9 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms; —SO₃ ⁻Me⁺,—PO(O⁻Me⁺)₂, —P(O)(OR₂)₂, —SO₂R₂, —CO—NH—R₂, —CONH₂, COOR₂, or Si(Me)₃,wherein Me⁺ is ═H⁺, ammonium or an alkali metal cation; or A is O—Y₁ andA′ is O—Y₂ forming a ketal structure in the 4 position; wherein Y₁ andY₂ are independently C₁-C₁₂alkyl, C₃-C₁₂alkenyl, C₃-C₁₂alkinyl,C₅-C₈cycloalkyl, phenyl, naphthyl or C₇-C₉phenylalkyl; or Y₁ and Y₂together form one of the bivalent groups —C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—,—CH(R₃₀₁)—CH₂—C(R₃₀₂)(R₃₀₃)—, —CH(R₃₀₂)—CH₂—C(R₃₀₁)(R₃₀₃)—,—CH₂—C(R₃₀₁)(R₃₀₂)—CH(R₃₀₃)—, o-phenylene, 1,2-cyclohexylidene,—CH₂—CH═CH—CH₂— or

 wherein R₃₀₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl orCH₂OR₃₀₄; R₃₀₂ and R₃₀₃ are independently hydrogen, methyl, ethyl, COOHor COO—(C₁-C₁₂)alkyl; and R₃₀₄ is hydrogen, C₁-C₁₂alkyl, benzyl or amonovalent acyl residue derived from an aliphatic, cycloaliphatic oraromatic monocarboxylic acid having up to 18 carbon atoms; and n is anumber from 2-20.